Process of manufacturing black sulfurized coloring-matters.



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ITED STATES PATENT OFFICE.

OTTO REINHARDT AND JULIUS HOERLIN, OF UERDIN GEN -ON-TH.'3- RHII lE, GERMANY, ASSIGNORS TO THE FIRM 0F CHEMISCHE FABRIKEN VORM. W'EILER-TER MEER, 0F UERDINGEN-ON-THERHINE, GERMANY.

PROCESS OF MANUFACTURING BLACK SULFURIZED COLORING-MATTERS.

Specification of Letters Patent.

Application flied December 5, 1906. Serial No. 346,511;

Patented May 21, 1912.

To all whom it may concern:

Be it known that We, Q'rro REINHARDT, doctor of philosophy, chemist, a subject of the Grand Duke of Baden and the German Emperor, residingat Niederstrasse 1, Uer: dingcn-on-the-Rhine, Rhine Province, Kingdom of Prussia, German Empire, and J ULIUs Honnmiv, doctor of philosophy, chemist, a

subjectof the Kingof Wurttemberg and the German Emperor, residing at Augustastrasse 3, Ue'rdingen-on-the-Rhine, Rhine Province, Kingdom of Prussia, German Empire, have jointly invented new and useful Improvements in Processes of Manufacturing Black Sulfurized Coloring-Matters, of,

which the followingis a specification.

The present process consists in, that certain amounts of aqueous solutions of alkali polysulfids are heated under pressure with aromatic nitro-hydroxy compounds.

,When compared With other processes for making sulfurized coloring matters this process shows an important difl'erence, that according to the resent invention the coloring matters are oitained in acr stallinc and solid state, whereas in the hit ierto known processes the coloring .matters are obtained in a paste and must beprecipitated from the resulting dissolutions, a process that is tedious and requires special apparatuses.

A further advantage is, that one can produce the same quantity of coloring matter as hithertowas only possible by the use of far larger amounts of alkaline polysulfids.

According to the present invention one can use as raw materials all. aromatic nit-rohydroxy compounds, especially those containing the nitro groups in meta position, for instance dinitrophenol or the sodium compound of dinitrophenol or oxydinitrodiphenylamins; of the dinitrodiphenylamins We have found as very suitable the products of the condensation of dinitroehlorbenzol "with para amidophenol or 'orthoamidophe- 1101. Also the reduction products of the said nitro compounds may be used, as in the process a reduction of the nitro group to the amide group will enter.

The following examples willdescribe the manner, inavhich our invention may be carried out.

(1.) We mix a paste of sodium salt of 80 kilograms dinitrophenol and 240 liters 'water with a solution of 140 kilograms of crystallized sodium sulfid and 56 kilograms sulfur in 50 liters water and place the mixture into a closed iron vessel provided with a steam-jacket and an a itator. The mixture isheated unto 90 degrees centigrade. After that temperature having been 0b 60 tained, one closes the vessel and heats with-- in about 30 minutes unto 130 to 150 degrees centigrade, which temperature is maintained for about 4"!) hours. The pressure in the vessel Will then be about lit-4 atmospheres. After the said time the pressure is reduced to the ordinary atmospheric pressure. In order to expel ammonia formed during the process, one heats, and may absorb the expolled ammonia in diluted acids. The color ing matter is obtained in crystalline and solid form and may then be separated from the liquor by filtration, and may then be pressed and dried. The'coloring mattcrob-t tained according to the described process has a greater dyeing power than the coloring matters obtained according to the hitherto known processes for manufacturing black sulfurized coloring matters and is obtained in a rcatcr proportion. of heating and concentration may be changed according to the special conditions. At a lower temperature a longer timeof heating will be required and inversely. The proportions may be increased until 2 molemiles of polysulfid to 1 molecule dinitrophenol. The best result will be obtained with 1.31.5molecules of polysulfid to 1 molecule dinitrophenol.

(2.) 55 kilograms p-oxy-o p,-dinil rodi-v phenylamin are put into a solution of 9G kilogramscrystallizcd sodium sulfid, 52 kilograms sulfur and 70 liters water and heated in a closed iron vessel, provided with a steamjackct and an agitator, for 4-8 hours to 3 i degrees centigrade. The coloring matter is obtained in a crystallinc'form. The mixture after having been cooled is diluted with Water, in order that the filtration may be carried out easily, and then separated from the liquor by filtration. The coloring matter is a dark-violet to black-blue powder, that is soluble in a diluted solution of sodium sulfid with a green color that is changed by the action of the air to dull blueblack. By varying the amount of sulfur, polysulfid, the temperature and the time of heating the coloring matter may be obtained Tcn'iperaturc, time 30' Cll 7 homologues.

Q use with a greenhuzl-c'siz slizuie. On -Hiring agents convert the coloring matter into a numlihiish muduct.

59 ltiloqi'rlnis n;i-i'liniti'oon'-ii1" liclilo1'--p-o.\' y tiphenylamin are put imo n solution of (i-(t kilograms sulfur in 120 kilogmms sultid of sodium and 100 liters writer and are heated in an iron pressure vessel under agitation to M0 HBO (leg ares ventigrmlefoi' several hours. The coloring inat 'tc." is separated in the same manner (lest-rihctl in the Example J'aia l a dark bluish powder with similar pro wrties as those of the coloring matter according; to limunple 2. Instead of O-Pfilll'llt]0-I11'-n'1'- iliclilorix ydiphenyluiuiii one may alsouse other substitution products of o--plini.-- tro-p-oxydiphenylamin, for instance lnomated derivatives, also the corrcspomling (lerivates of 0-HlllltlOPllQllOl or the higher With these substances one obtains variations in the shade of the coloring matter that is however always obtained in :1 F-Olitl state.

l Vhut we claim as our invention, and desire to secure by Letters Patent, is

Lv'lhe process of manufacturing black s irlurizecl coloring matters which consists in heating, under pressure, aqueous solntions of alkali polysulfids with aromatic nitro-hydroxy compounds;v

Q. The process of ma hlzuzl; or green-black 'sulfu-r ized coloring matters which eonsists in heating an amount correspmuling to between 1.5 molecules and molecules of an alkali polysulfid in-an aqueous solution under pressure with an amount corresponding to one imolecule of oxyrtinitrophenylamin. i v

ln witness whereof we have hereunto signed. our names this 15th day of Nov.

1906, in'- the presence of two subscribing witnesses.

' OTTO REINHARDT. JULIUS HOERLIN. Witnesses 'W. lmuon VVALLAon, HnuMAnn MtJLLIcu.

cturing blue I 

